Process for producing tetrafluoroethylene from perfluorocarbon having at least three carbon atoms



3 SheetsSheet l FARLOW May 24, 1955 M.

PROCESS FOR PRODUCING TETRAFLUOROETHYLENE FROM PERFLUOROCARBON HAVING AT LEAST THREE CARBON ATOMS Filed Nov. 6. 1953 m E w W O I L R A F a TR W. 55226 K m w M m, P -H 55202,: $5226 2. Q t I A v V. $565 m. v mzfiwzfiomgdku $955 32 ":3; Z Q50: v F ozrvfifimw h. ,(2 m $5233 $5205: a o. 5 6528 w. :22 538E i) n ATTORNEY May 24, 1955 M. w. FARLOW 2,709,182

PROCESS FOR PRODUCING TETRAFLUOROETHYLENE FROM PERFLUOROCARBON HAVING AT LEAST THREE CARBON ATOMS Filed Nov. 6, 1953 5 Sheets-Sheet 2 PRODUCT OUT WATER JACKET Cu ELECTRODE HOLDER FLEXIBLE lNSULATING CONNECTION FIG.2 5 5 ,GRAPHITE ELECTRODE {WATER JACKET WATER JACKET CATHODE()/7E INVENTOR GAS m MARK w. FARLOW ATTORNEY May 24, 1955 w, L w 2,709,182

PROCESS FOR PRODUCING TETRAFLUQROETHYLENE FROM PERFLUORQCARBON HAVING AT LEAST THREE CARBON ATQMS Filed Nov. 6, 1953 5 Sheets-Sheet 3 EXIT GASES R E s N E D N o C ANODE WATER JACKET CATHODE P) Cu ELECTRODE HOLDER GRAPHITE ELECTRODE LlQUiD FLUOROCARBQN INVENTOR MARK W. FARLOW BY w ATTORNEY PROCESS FOR PRGDUCING TETRAFLUORO- ETHYLENE FROM PERFLUOROCARBON gAglgG AT LEAST THREE CARBON Mark W. Farlow, Holly Oak, DeL, assignor to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware Application November 6, 1953, Serial No. 390,461

13 Claims. (Cl. Z60-653) This invention relates to a new process for the preparation of tetrafluoroethylene.

C., should not exceed one second and preferably is in the range from about 0.001 second to 0.1 second. The

critical.

Tetrafluoroethylene is an unsaturated fluorocarbon of considerable utility in various applications. In particular, it is very useful in the form of its polymers where it has achieved commercial success. Even wider use for this fluorocarbon could be attained if more economical methods for its preparation could be devised, since even in the best of the heretofore known methods for its preparation, it is not possible to obtain high yields of the desired tetrafluoroethylene.

This invention has as an object a more economical process for the preparation of tetrafluoroethylene. Other objects will appear hereinafter.

These objects are accomplished by the present invention wherein a fluorocarbon, i. e., a perfluorohydrocarbon, of the formula CxFy which is liquid at room temperature or lower, in which x and y are positive whole numbers, with x being at least 3, and in which the ratio of y to x is less than 2.721 is pyrolyzed by heating at a temperature of at least l500 C. In a preferred modification of the invention substantially complete conversion of the starting fluorocarbon to tetrafluoroethylene is accomplished by separating out the tctrafluoroethylene and recycling the remainder of the fluorocarbon reaction mixture.

The pyrolysis of the fluorocarbons of the above formula can be accomplished by passing the fluorocarbon through a reaction zone heated to a temperature of at least 1500 C. and preferably at 20004000 C. The reaction zone can be a hollow tube of refractory material heated externally to the desired temperature by conventional means, or the liquid or gaseous perfluorocarbon li step by a process described in my concurrently reactant can be exposed to an electric arc. Especially good results are obtained by passing the fluorocarbon through an are produced between carbon electrodes, in which case the temperature is estimated tobe between 2500 and 4000 C. The carbon arc is especially suitable action mixture can b li h d by ti l for pyrolyzing iiuorocarbons having a ratio of fluorine to carbon of more than 2 to 1, since with such fluorocarbons it is beneficial to have carbon present in the reaction zone to react with the excess of fluorine. On the other hand, particularly when the ratio of fluorine to carbon in the fluorocarbon reactant is two or less, electrodes of other materials of construction can be used to produce the electric arc. For example, electrodes of tungsten or of zirconia can be used.

rapid quenching of the reaction mixture is essential to practical operation in the process of this invention.

The absolute pressure in the reaction zone is not Satisfactory results can be obtained at pressures as low as 1 mm. of mercury as well as at atmospheric pressure and even under superatmospheric pressure. In general, low pressures are preferred when passing vapors of a fluorocarbon through a carbon arc, since the operation of the arc becomes more diflicult with higher pressures. Superatmospheric pressures are useful when it is desired to pyrolyze low boiling fluorocarbons in an arc in which the electrodes are submerged in the liquid fluorocarbon. The rate of passage of the fluorocarbon reactant through the reaction zone can vary widely in the process of this invention since the rate of flow is not critical. The optimum rate or flow depends on the throughput of electric power in the are, or on the capacity of the external heating means being used. In general, the greater the amount of electric current provided to the are or the greater the amount of external heat Practical conversions to tetrafluoroethylene can be obdemonstrated that quenching of the product from the reaction temperature to a temperature no higher than 400 C. is essential to the success of the process. The time during which the reaction mixture is cooled to below the decomposition temperature of tetrafluoroethylene,

i. e., the time from pyrolysis temperature to below 400 .3.

supplied the greater is the rate at which the fluorocarbon reactant can be pyrolyzed.

When an electric arc is used as a source of heat, the arc can be operated at low or high voltage and with either direct or alternating current. Good results in the process of this invention are obtained when the pyrolysis is carried out in electric arcs produced between carbon electrodes with electric current of 10 to 50 volts and of 10 to 30 amperes. However, the process is not limited to the use of this narrow range of voltage and amperage.

The product of the pyrolysis of the fluorocarbons of y the above defined composition is normally a mixture of of other perfluorocarbons, depending on the particular reaction conditions employed. The carbon tetrafluoride and hexafluoroethane formed as oy-products have les'than three carbon atoms. These fluorocarbons are in turn converted to tetrafluoroethylene during the remethods, for example, by careful fractional distillation. The boiling points of hexafluoroethane and tetrafluoroethylene are quite close together, and, when appreciable quantities of hexafluoroethane are produced, it is necessary to use very eflicient fractionating columns to separate such mixtures. These can also be separated by selective solvent extraction or by selective adsorption on solids. However, because of its inertness, the presence of small amounts of hexafluoroethane does not interfere with the use of tetrafiuoroethylene for most purposes, including polymerization.

The process of this invention is further illustrated by the following examples. In Examples I to III, the pyrolysis is carried out by passing the fluorocarbon vapor through a carbon are. A flow sheet of a preferred type of equipment for pyrolysis of perfluoro compounds in a carbon arc is shown in Figure l. The gas lines are of copper tubing. In a typical operation, the perfluorocarbon reactant is contained in cylinder -or tank 1. Valves 2, 4, 15 and 19 are closed, and valves 7 and 12 are opened. T he apparatus is evacuated by means of pump 13 to remove the air, trap 10 is cooled with liquid nitrogen, valve '7 is closed, argon (Or other inert gas) is admitted through valve 4- to the desired operating pressure, and pressure controller 11 is set to maintain that desired pressure. The are 6, is struck, the reactant gas is passed t: rough the are at the desired rate (flowrneter 3) and the product is condensed in. trap 10. During operation the arc inlet pressure (manometer 5) will be appreciably higher than the exit pressure (manometer 9) because of the constriction involved in the arc passages. When it is desired to stop the reaction, the arc current is cut oif, valves 2 and 12 are closed, valve 7 is opened, cylinder 8 is cooled with liquid nitrogen, trap 1.0 is allowed to warm to room temperature, and the volatile product is distilled into cylinder 8. Finally. if desired, cylinder 8 can be pumped to remove traces of argon or other noncondensables, after which the cylinder valve is closed and the product is allowed to warm to room temperature.

in continuous operation the trap 19 is connected through valve 15 to fractionating column 15 which sep arates, so far as possible, the tetrafluorocthylene from the eiiiux from the arc, sends the tctrafiuoroethylene of greater or less purity, depending on the grade desired, to tetraliuorosthylcnc storage 18 and returns the remaining fluorocarbon products through valve 19 and flowmeter 3 to the are 6. The separation of tetrafiuoroethylene from other fiuorocarbons, even hexafluoroethane, is readily effected in a highly efficient fractionating column.

A detail of the are 6 used with gaseous reactants is shown in Figure 2. The electrodes consist of graphite cylinders. water jackets are made of electrically non-conductive material. The are is struck by contacting the two electrodes. Thereafter, the electrode gap is controlled to effect the requisite current. A direct current voltage is applied across the electrode in a conventional manner.

A detail of apparatus having a carbon arc submerged in liquid fluorocarbon reactant is shown in Figure 3. in this apparatus the arc is operated as described in the preceding paragraph Example I Octafiuoropropane is passed through a carbon tube are of 0.1 inch. internal diameter (Figures 1 and 2')v at a rate of 67 per hour, at an arc inlet pressure of 32 mm. of mercury, absolute, and at an exit pressure of 7 mm. of mercury (absolute). The are is operated at 20-25 volts and 20 amperes. The products are cooled: from are temperature to below 400 C. in less than about 0.] second. The ratio. by volume, of fiuorocarbnns exit is as follows: tctrafiuoroethylene, 59; carbon tetrafluoride, 2G; octafluoropropane, 20; hX.' lllbL0l0 ethane, 5; and hexafiuoropropene, 5.

Example II Hcxalluoropropene is passed through a carbon are (Figures 1 and 2) at a rate of 75 g. per hour, at an arc inlet pressure of 38-42 mm. of mercury, absolute, and at an exit pressure of 7 mm. of mercury (absolute). The are is operated at 26-25 volts and 20 amperes direct current. The quenching is rapid, the time from reaction temperature to below 460 C. being less than 0.1 second. The ratio, by volume, of the products in the exit gas is: tetrafluoroethylene, 50; hexafiuoropropene, 40; carbontetrafluoride, hexafiuoroethane, 2; and octafiuoropropane, 1.

Example III A mixture of perfluorodimethylcyclohexane isomers, CaFis, prepared by exhaustive fiuorination of mixed xylenes, is passed through a carbon are similarto that shown in Figure 2, at a pressure of about 10 mm. of

mercury, absolute, at a rate of 20 g. per hour. The

are is operated with direct current of 20-30 volts and 12-21 amperes. The time from reaction temperature to below 400 C. is less than 0.5 second. After three recyclings with intermediate rapid quenching and isolation of tetrafluoroethylene, the final products are 50 volumes tetrafluoroethylene, 30 volumes carbon tetrafluoride, and 20 volumes higher fluorocarbons.

The following example illustrates the pyrolysis of a liquid perfluorocarbon by means of a submerged carbon are at atmospheric pressure.

Example IV A carbon arc is operated under the surface of liquid perfluerodimethylcyclohexane (the mixture of isomers described in Example III) at atmospheric pressure, in a vessel fitted with a reflux condenser cooled by a liquid maintained at -75 to C. and a take-oft at the top of the condenser for the recovery of uncondensed gaseous products (Figure 3). With the are produced by a direct current of 18 volts and 12-13 amperes, the liquid perfluorocarbon refluxes vigorously thus giving very rapid quenching of the reaction products and the gas evolution is 4.6 liters per hour, measured at room temperature and atmospheric pressure. The gas contains, in addition to a trace of the starting material, 25 molar per cent of tetrafluoroethylene, the remainder being a mixture consisting mainly of carbon tetrafluoride, hexafiuoroethane, hexafluoropropene and octafiuoropropane.

The examples have illustrated the process of this invention with specific reference to certain fiuorocarbons. However, the invention is generically applicable to fluorocarbons, i. e., perfluorohydrocarbons, having the formula CrFy, wherein x and y are positive whole numbers, x is at least 3 and the ratio of y to x is less than 2.7:1. Specific examples of other perfluorocarbons of this type which are operable include perfluoro-l,3-butadiene, octafluorocyclobutane, C41 8; decafiuorobutane, C4F1o; and the perfluorocarbons obtained by exhaustive fiuorination of petroleum fractions, e. g., perfluorinated lubricating oil, C21F44, and perfluorinated kerosene having from 10 to 14 carbon atoms.

The fluorocarbon being pyrolyzed, and any carbon used in the process, are preferably substantially anhydrous. In particular, care should be taken to dehydrate the carbon prior to reaction, since carbon, especially of the active or absorbent variety, can con tain significant amounts of water even at high temperature.

The examples have illustrated the process of this invention by pyrolysis of the fluorocarbons in electric arcs. The use of arcs, particularly between carbon electrodes, is a preferred way of carrying out this process. However, the pyrolysis can be carried out in other types of electrodes, for example, tungsten and zirconia electrodes; and in reaction vessels made of carbon or other forms of refractory materials. When carbon reactors or reactors packed with carbon are used, any form of carbon, either amorphous or crystalline, is suitable. Thus, there can be used coal, graphite, diamond, charcoal and the various forms of carbon black, such as lamp black, acetylene black, bone black, etc. The powdered forms of carbon are, of course, used as packing in the form of pellets or supported on supports such as coke. In general, best results are obtained with active carbon, of which many well-known varieties are available commercially. In general, active carbon is very finely divided porous carbon having a total surface area of at least 20 square meters per gram (Hassler, Active Carbon, Chemical Publishing Company, N51, page 127).

Important advantages of the process of this invention over the hitherto known methods of preparing tetrafiuoroethylene reside in the fact that any of the wide variety. of perfluorocarbons having the formula described previously can be pyrolyzed to high yields of tetrafluoroethylene. Especially high yields of this desired material are attained by separating the tetrafluoroethylene from the reaction mixture obtained by one pass of the perfiuoro carbon through the pyrolysis zone and then recycling the by-products. In this way, substantially complete conversion of the starting material to the desired tetrafluoroethylene is attained.

The foregoing detailed description has been given for clearness of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described for obvious modifications will occur to those skilled in the art.

What is claimed is:

1. A process for the preparation of tetrafluoroethylene wherein a fluorocarbon of at least three carbons and of melting point no higher than 25 C. is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products.

2. A process for the preparation of tetrafluoroethylene wherein a fluorocarbon of at least three carbons and of melting point no higher than 25 C. is pyrolyzed by heating the same in a carbon arc, the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products.

3. A process for the preparation of tetrafluoroethylene wherein an open chain fluorocarbon of at least three carbons and of melting point no higher than 25 C. is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products.

4. A process for the preparation of tetrafluoroethylene wherein a ring fluorocarbon of at least three carbons and of melting point no higher than 25 C. is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products.

5. A process for the preparation of tetrafluoroethylene wherein octafluoropropane is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafiuoroethylene is removed from the pyrolysis products.

6. A process for the preparation of tetrafluoroethylene wherein hexafluoropropene is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products.

7. A process for the preparation of tetrafluoroethylene wherein a mixture of perfluorodimethylcyclohexanes is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products.

8. A process for the preparation of tetrafluoroethylene wherein a fluorocarbon of at least three carbons and of melting point no higher than 25 C. is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products, the remainder of which is again exposed to pyrolysis.

9. A process for the preparation of tetrafluoroethylene wherein an open chain fluorocarbon of at least three carbons and of melting point no higher than 25 C. is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products, the remainder of which is again exposed to pyrolysis.

10. A process for the preparation of tetrafluoroethylene wherein a ring fluorocarbon of at least three carbons and of melting point no higher than 25 C. is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products, the remainder of which is again exposed to pyrolysis.

11. A process for the preparation of tetrafluoroethylene wherein octafluoropropane is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products, the remainder of which is again exposed to pyrolysis.

12. A process for the preparation of tetrafluoroethylene wherein hexafluoropropene is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products, the remainder of which is again exposed to pyroly- 13. A process for the preparation of tetrafluoroethylene wherein a mixture of perfluorodimethylcyclohexane is pyrolyzed by heating the same to a temperature of at least 1500 C., the pyrolysis mixture is rapidly cooled below 400 C., and the tetrafluoroethylene is removed from the pyrolysis products, the remainder of which is again exposed to pyrolysis.

References Cited in the file of this patent UNTTED STATES PATENTS 1,023,783 Knapp Apr. 16, 1912 1,056,045 Muray Mar. 18, 1913 2,480,560 Downing et al. Aug. 30, 1949 2,551,573 Downing et al. May 8, 1951 2,664,449 Miller Dec. 29, 1953 2,674,631 Miller et al. Apr. 6, 1954 2,676,145 Weisz et al. Apr. 20, 1954 

1. A PROCESS FOR THE PREPARATION OF TETRAFLUOROETHYLENE WHEREIN A FLUOROCARBON OF AT LEAST THREE CARBONS AND OF MELTING POINT NO HIGHER THAN 25* C. IS PYROLYZED BY HEATING THE SAME TO A TEMPERATURE OF AT LEAST 1500* C., THE PYROLYSIS MIXTURE IS RAPIDLY COOLED BELOW 400* C., AND THE TETRAFLUOROETHYLENE IS REMOVED FROM THE PYROLYSIS PRODUCTS. 